Fused-Pentagon Carbon Cages in Chloro and Trifluoromethyl Derivatives of C: Non-IPR CCl, C(CF), and Nonclassical C()Cl.

High-temperature chlorination of conventional IPR C can produce chloro derivatives of non-IPR C by skeletal transformations via Stone-Wales rearrangements (SWRs) of the carbon cage. We report the synthesis and structure elucidation of non-IPR CCl and nonclassical C()Cl. The present isolation of CCl hints at the possibility that the same product in the previously reported chlorine-doped arc-discharge synthesis could have, likewise, resulted from the initially formed IPR C. C()Cl is the first chloride containing a nonclassical carbon cage with one heptagon and 13 pentagons known previously only in a CF derivative. Additionally, trifluoromethylation of non-IPR chlorides revealed the formation of C(CF) with a new non-IPR carbon cage and unusual trifluoromethylation pattern. Thereby, the number of different, structurally confirmed non-IPR carbon cages of C now reaches eight.